Efficient bio-refractory industrial wastewater treatment with mitigated membrane fouling in a membrane bioreactor strengthened by the micro-scale ZVI@GAC galvanic-cells-initiated radical generation and coagulation processes.

Micro-scale ZVI@GAC-based iron-carbon galvanic-cells (ZVI@GACs) were prepared with the Ca-Si-H/Ca-H formation process and first applied to initiate radical generation and coagulation processes in MBR for treating bio-refractory industrial wastewater (IWW). Batch tests revealed the H2O2 production (0.19-0.28 mg/L) and •OH generation (p-CBA decay, k1 = 0.040 min-1) in ZVI@GACs-dosed system (packing volume of 5%) under aeration. Adoption of ZVI@GACs into aerobic activated sludge process (ZVI@GACs/AS) enhanced TOC degradation (k2) and phenolic compounds (PHENs) destruction (k3). ZVI@GACs/AS at ZVI@GACs packing volume of 5%, 10% and 20% improved k2 from 0.11 h-1 (bare AS) to 0.17, 0.21 and 23 h-1 and k3 from 0.24 h-1 to 0.36, 0.49 and 0.57 h-1, respectively. The oxygen uptake rate (OUR) and 15-min acute bio-toxicity demonstrated that the bio-toxicity of IWW was reduced and the activity of biomass was enhanced in the ZVI@GACs/AS system. In MBR, ZVI@GACs at packing volume of 10% enhanced COD and PHENs removal by 14% and 22%, respectively. Membrane fouling cycle was prolonged by 71%. The accumulations of EPS-proteins, EPS-polysaccharides, SMP-proteins and SMP-polysaccharides were reduced by 6%, 67%, 27% and 60%, respectively. Fourier transform infrared spectroscopy (FTIR) confirmed the oxidation of SMP-polysaccharides in ZVI@GACs-MBR. The iron ions released from ZVI@GACs showed inhibition on the secretion of SMP-/EPS-proteins. Floc particle size distribution (PSD) and X-ray diffraction (XRD) spectrum confirmed that the coagulation effects of Fe(OH)3 and FeOOH triggered by Fe3+ increased the sludge floc size and contributed to membrane fouling mitigation. Genus Enterococcus was enriched in MBR with the destruction of PHENs by the ZVI@GACs-initiated radical generation process. The findings of this study confirmed successful development and adoption of ZVI@GACs into MBR for bio-refractory IWW treatment. It also provided an in-depth understanding on the mechanisms of ZVI@GACs-MBR system.